Support, zeolite membrane complex, method of producing zeolite membrane complex, and separation method

ABSTRACT

A porous cylindrical support for use in supporting a zeolite membrane has a generally cylindrical inside surface having a central axis extending in the longitudinal direction and a generally cylindrical outside surface that surrounds the inside surface. A zeolite membrane is formed on the outside surface. A maximum value A and a minimum value B of a support thickness in a circumferential direction satisfy (A−B)/(A+B)≤0.3 in at least part of the support in the longitudinal direction, the support thickness being a radial distance between the inside surface and the outside surface. By reducing a variation in support thickness, it is possible to improve uniformity in the thickness of the zeolite membrane formed on the support.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of U.S. application Ser. No. 17/201,269,filed Mar. 15, 2021, which is a continuation application ofInternational Application No. PCT/JP2019/030538, filed on Aug. 2, 2019.The contents of these applications are incorporated herein by referencein their entirety.

TECHNICAL FIELD

The present invention relates to a support used to support a zeolitemembrane, a zeolite membrane complex including the support, a method ofproducing the zeolite membrane complex, and a method of separating amixture of substances with use of the zeolite membrane complex.

BACKGROUND ART

Various studies and developments are currently underway on forming azeolite membrane on a porous support to obtain a zeolite membranecomplex and using the molecular-sieving function of the zeolite inapplications such as the separation of specific molecules and theadsorption of specific molecules.

For example, Japanese Patent Application Laid-Open No. H09-71481(Document 1) discloses a ceramic support that is used as a support of azeolite membrane. Japanese Patent Application Laid-Open No. 2012-66241(Document 2) and International Patent Publication WO/2007/105407(Document 3) disclose zeolite membrane complexes in which a zeolitemembrane is formed by hydrothermal synthesis on the outside surface of acylindrical (tubular) ceramic support.

In general, a cylindrical ceramic support (hereinafter, simply referredto as a “support”) is produced by extrusion molding and surfacegrinding. Specifically, first, green body prepared by kneading apredetermined raw material is supplied to and extruded from a mold whilebeing molded into a cylindrical form. Then, a generally cylindricalcompact extruded from the mold is fired, and thereafter the outsidesurface of the fired compact is grinded so as to have an almost perfectcircular shape in cross section. This forms the aforementioned support.

In the preparation of this cylindrical support, the support may have avarying radial thickness in the circumferential direction due to factorssuch as a variation in the rate of supply of the green body to the mold.The variation in the radial thickness of the support may also be causedby other factors such as imbalances in the amount of grinding duringgrinding of the outside surface. Specifically, when a cylindricalcompact is extruded from the mold, the cylindrical compact may extendlaterally by gravity so as to have inside and outside surfaces that havegenerally horizontally-long-elliptical shapes in cross section. In thiscase, the amount by which the lateral sides of the support are grindedbecomes greater than the amount by which the vertical sides of thesupport are grinded, in order to make the cross-sectional shape of theoutside surface close to a perfect circle. As a result, the support ismade to a smaller lateral thickness than the vertical thickness.

If a zeolite membrane is formed on a cylindrical support having such avarying thickness, variations will increase in the amount of seedcrystals supplied per unit area to the surface of the support, andaccordingly uniformity will decrease in the membrane thickness of thezeolite membrane. It is thus difficult to form a dense and thin zeolitemembrane with high yields. However, no studies have been made from theviewpoint of the degree to which it is necessary to suppress variationsin the thickness of a support in order to form a dense and thin zeolitemembrane.

SUMMARY OF INVENTION

The present invention is directed to a porous cylindrical support thatis used to support a zeolite membrane. A support according to apreferable embodiment of the present invention includes a generallycylindrical inside surface having a central axis extending in alongitudinal direction and a generally cylindrical outside surface thatsurrounds the inside surface. A maximum value A and a minimum value B ofa support thickness in a circumferential direction satisfy(A−B)/(A+B)≤0.3 in at least part of the support in the longitudinaldirection, the support thickness being a radial distance between theinside surface and the outside surface. Accordingly, it is possible toimprove uniformity in the membrane thickness of the zeolite membrane.

Preferably, the maximum value A and the minimum value B satisfy(A−B)/(A+B)≤0.3 along an entire length of the support in thelongitudinal direction.

Preferably, the maximum value A and the minimum value B satisfy(A−B)/(A+B)≤0.2 in at least part of the support in the longitudinaldirection.

Preferably, the inside surface has a mean radius X and roundness Y thatsatisfy Y/X≤0.5 in the at least part of the support in the longitudinaldirection.

Preferably, the support is formed of a ceramic sintered compact.

The present invention is also directed to a zeolite membrane complex. Azeolite membrane complex according to a preferable embodiment of thepresent invention includes the aforementioned support and a zeolitemembrane formed on the support.

Preferably, a maximum number of membered rings in a zeolite of thezeolite membrane is less than or equal to 8.

Preferably, the zeolite membrane has a thickness less than or equal to 1μm.

The present invention is also directed to a method of producing azeolite membrane complex. A method of producing a zeolite membranecomplex according to a preferable embodiment of the present inventionincludes a) preparing seed crystals, b) depositing the seed crystals onthe aforementioned support, and c) forming a zeolite membrane on thesupport by growing a zeolite from the seed crystals by hydrothermalsynthesis.

The present invention is also directed to a separation method. Aseparation method according to a preferable embodiment of the presentinvention includes d) preparing the aforementioned zeolite membranecomplex, and e) supplying a mixture of substances that includes aplurality of types of gases or liquids to the zeolite membrane complexand separating a high-permeability substance in the mixture ofsubstances from the mixture of substances by causing thehigh-permeability substance to permeate through the zeolite membranecomplex.

Preferably, the mixture of substances includes one or more kinds ofsubstances including hydrogen, helium, nitrogen, oxygen, water, watervapor, carbon monoxide, carbon dioxide, nitrogen oxide, ammonia, sulfuroxide, hydrogen sulfide, sulfur fluoride, mercury, arsine, hydrocyanicacid, carbonyl sulfide, C1 to C8 hydrocarbons, organic acid, alcohol,mercaptans, ester, ether, ketone, and aldehyde.

These and other objects, features, aspects and advantages of the presentinvention will become more apparent from the following detaileddescription of the present invention when taken in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a sectional view of a zeolite membrane complex;

FIG. 2 is an enlarged sectional view of the zeolite membrane complex;

FIG. 3 is a sectional view of a support;

FIG. 4 is a diagram illustrating a procedure for producing the zeolitemembrane complex;

FIG. 5 is a diagram illustrating a zeolite membrane complex in thecourse of production;

FIG. 6 is a diagram illustrating a separation apparatus; and

FIG. 7 is a diagram illustrating a procedure for separating a mixture ofsubstances.

DESCRIPTION OF EMBODIMENTS

FIG. 1 is a sectional view of a zeolite membrane complex 1. FIG. 2 is asectional view illustrating part of the zeolite membrane complex 1 inenlarged dimension. The zeolite membrane complex 1 includes a poroussupport 11 and a zeolite membrane 12 formed on the support 11. In FIG. 1, the zeolite membrane 12 is illustrated with bold lines. In FIG. 2 ,the zeolite membrane 12 is cross-hatched. The membrane thickness of thezeolite membrane 12 illustrated in FIG. 2 is thicker than the actualmembrane thickness.

The support 11 is a cylindrical member. The support 11 is a porousmember that is permeable to gases and liquids. The support 11 has aninside surface 113 that is generally cylindrical about a central axis J1extending in a longitudinal direction (i.e., a right-left direction inFIG. 1 ), and an outside surface 112 that is generally cylindrical andsurrounds the inside surface 113. The central axis J1 as used hereinrefers to a central axis of a virtual cylinder arranged so as tocircumscribe the inside surface 113. The outside surface 112 is locatedoutward of the inside surface 113 in a radial direction about thecentral axis J1 (hereinafter, also simply referred to as the “radialdirection”) and surrounds the inside surface 113. The outside surface112 has the zeolite membrane 12 formed thereon. The zeolite membrane 12covers approximately the entire outside surface 112 of the support 11.In the following description, a generally columnar space locatedradially inward of the inside surface 113 is referred to as an “innerflow path 111.”

The support 11 has a length (i.e., length in the right-left direction inFIG. 1 ) of, for example, 10 cm to 200 cm. The support 11 has an outerdiameter of, for example, 0.5 cm to 30 cm. A distance in the radialdirection between the inside surface 113 and the outside surface 112 ofthe support 11 (hereinafter, also referred to as a “support thickness”)is, for example, in the range of 0.1 mm to 10 mm. Surface roughness (Ra)of the support 11 is, for example, in the range of 0.1 μm to 5.0 μm andpreferably in the range of 0.2 μm to 2.0 μm.

As the material for the support 11, various substances (e.g., ceramic ormetal) may be employed as long as they are chemically stable during thestep of forming the zeolite membrane 12 on the surface of the support11. In the present embodiment, the support 11 is formed of a ceramicsintered compact. Examples of the ceramic sintered compact that isselected as the material for the support 11 include alumina, silica,mullite, zirconia, titania, yttrium, silicon nitride, and siliconcarbide. In the present embodiment, the support 11 contains at least oneof alumina, silica, and mullite.

The support 11 may contain an inorganic binder. The inorganic binder maybe at least one of titania, mullite, easily sinterable alumina, silica,glass frit, clay minerals, and easily sinterable cordierite.

A mean particle diameter of the support 11 in the vicinity of thesurface where the zeolite membrane 12 is formed is smaller than a meanparticle diameter of the support 11 in the other portions. To achievethis structure, the support 11 has a multilayer structure. When thesupport 11 has a multilayer structure, the material for each layer maybe any of the materials described above, and each layer may be formed ofthe same material or may be formed of a different material. The meanpore diameter of the support 11 can be measured using an apparatus suchas a mercury porosimeter, a perm porometer, or a nano-perm porometer.

The mean pore diameter of the support 11 is, for example, in the rangeof 0.01 μm to 70 μm and preferably in the range of 0.05 μm to 25 μm. Ina pore size distribution of the support 11 in the vicinity of thesurface where the zeolite membrane 12 is formed, D5 is, for example, inthe range of 0.01 μm to 50 μm, D50 is, for example, in the range of 0.05μm to 70 μm, and D95 is, for example, in the range of 0.1 μm to 2000 μm.A porosity of the support 11 in the vicinity of the surface where thezeolite membrane 12 is formed is, for example, in the range of 25% to50%.

FIG. 3 is a diagram illustrating a section of the support 11 that isperpendicular to the longitudinal direction (i.e., section perpendicularto the central axis J1). In FIG. 3 , a position at which the distance inthe radial direction between the inside surface 113 and the outsidesurface 112 of the support 11 becomes a maximum is indicated by arrows,and the support thickness at this position is assumed to be a maximumvalue A of the support thickness. A position at which the distance inthe radial direction between the inside surface 113 and the outsidesurface 112 of the support 11 becomes a minimum is also indicated byarrows, and the support thickness at this position is assumed to be aminimum value B of the support thickness.

The maximum value A and the minimum value B of the support thickness inone cross-section of the support 11, which is perpendicular to thecentral axis J1, satisfy “(A−B)/(A+B)≤0.3.” In other words, thisrelation between the maximum value A and the minimum value B issatisfied in at least part of the support 11 in the longitudinaldirection. Preferably, this relation between the maximum value A and theminimum value B is satisfied along the entire length of the support 11in the longitudinal direction (i.e., in each cross-section in thelongitudinal direction).

Preferably, the maximum value A and the minimum value B of the supportthickness satisfy (A−B)/(A+B)≤0.2 in at least part of the support 11 inthe longitudinal direction. More preferably, this relation between themaximum value A and the minimum value B of the support thickness issatisfied along the entire length of the support 11 in the longitudinaldirection (i.e., in each cross-section in the longitudinal direction).

A mean radius X and roundness Y of the inside surface 113 of the support11 in the above one cross-section perpendicular to the central axis J1satisfy Y/X≤0.5. In other words, this relation between the mean radius Xand the roundness Y is satisfied in at least part of the support 11 inthe longitudinal direction. Preferably, this relation between the meanradius X and the roundness Y is satisfied along the entire length of thesupport 11 in the longitudinal direction (i.e., in each cross-section inthe longitudinal direction). The mean radius X in one cross-section ofthe support 11 is an arithmetical mean of the maximum radius and theminimum radius in this cross-section. The roundness Y is obtained inconformity with JIS-B-0621. Specifically, in this cross-section, a roughcircle (i.e., circular form) serving as the inside surface 113 issandwiched between two concentric geometric circles, and a differencebetween the radii of these two geometric circles, obtained when theinterval between the two geometric circles becomes a minimum, isregarded as the roundness Y.

The zeolite membrane 12 is a porous membrane with small pores. Thezeolite membrane 12 can be used as a separation membrane that separatesa specific substance from a mixture of substances including a pluralityof types of substances, using its molecular sieving function. Thezeolite membrane 12 is less permeable to the other substances than tothe specific substance. In other words, a permeance of the othersubstances through the zeolite membrane 12 is lower than a permeance ofthe above specific substance through the zeolite membrane 12.

The zeolite membrane 12 has a membrane thickness of, for example, 0.05μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to10 μm. The membrane thickness of the zeolite membrane 12 as used hereinrefers to a minimum value for the distance from the surface of thesupport 11 to the surface of the zeolite membrane 12 (i.e., minimumthickness) in the overall zeolite membrane 12 with the exception ofdefective portions. The same also applies to the following description.In the present embodiment, the membrane thickness of the zeolitemembrane 12 is less than or equal to 1 μm. A mean membrane thickness ofthe zeolite membrane 12 is preferably less than or equal to 5 μm, morepreferably less than or equal to 3 μm, and yet more preferably less thanor equal to 2 μm. Increasing the membrane thickness of the zeolitemembrane 12 improves the selectivity. Reducing the thickness of thezeolite membrane 12 increases the permeance. Surface roughness (Ra) ofthe zeolite membrane 12 is, for example, less than or equal to 5 μm,preferably less than or equal to 2 m, and more preferably less than orequal to 1 μm. Yet more preferably, the surface roughness (Ra) of thezeolite membrane 12 is less than or equal to 0.5 μm

Examples of the zeolite of the zeolite membrane 12 include a zeolite inwhich atoms (T atoms) located in the center of an oxygen tetrahedron(TO₄) constituting the zeolite are composed of only Si or composed of Siand Al, an AlPO-type zeolite in which the T atoms are composed of Al andP, an SAPO-type zeolite in which the T atoms are composed of Si, Al, andP, an MAPSO-type zeolite in which the T atoms are composed of magnesium(Mg), Si, Al, and P, and a ZnAPSO zeolite in which the T atoms arecomposed of zinc (Zn), Si, Al, and P. Some of the T atoms may bereplaced by other elements.

When n represents a maximum number of membered rings in the zeolite ofthe zeolite membrane 12, an arithmetical mean of the major and minoraxes of an n-membered ring pore is assumed to be a mean pore diameter.The n-membered ring pore as used herein refers to a pore whose number ofoxygen atoms that are bonded to T atoms and make a ring structure is n.When the zeolite has a plurality of n-membered ring pores where n is thesame number, an arithmetical mean of the major and minor axes of alln-numbered rings is assumed to be the mean pore diameter of the zeolite.In this way, the mean pore diameter of the zeolite membrane is uniquelydetermined by the framework structure of the zeolite and can be obtainedfrom a value disclosed in “Database of Zeolite Structures” [online] bythe International Zeolite Association on the Internet<URL:http://www.iza-structure.org/databases/>.

The mean particle diameter of the zeolite membrane 12 is preferablygreater than or equal to 0.2 nm and less than or equal to 0.8 nm, morepreferably greater than or equal to 0.3 nm and less than or equal to 0.6nm, and yet more preferably greater than or equal to 0.3 nm and lessthan or equal to 0.5 nm. The mean particle diameter of the zeolitemembrane 12 is smaller than the mean pore diameter of the support 11 inthe vicinity of the surface where the zeolite membrane 12 is formed.

There are no particular limitations on the type of the zeolite of thezeolite membrane 12, but from the viewpoint of increasing the CO₂ fluxand improving the CO₂ selectivity, a maximum number of atoms in the ringof the zeolite is preferably less than or equal to 8 (e.g., 6 or 8). Thezeolite membrane 12 is, for example, a DDR-type zeolite. In other words,the zeolite membrane 12 is a zeolite membrane composed of a zeolitehaving a framework type code “DDR” assigned by the International ZeoliteAssociation. In this case, the zeolite of the zeolite membrane 12 has anintrinsic pore diameter of 0.36 nm×0.44 nm and a mean pore diameter of0.40 nm.

For example, the zeolite membrane 12 may be any of the following typesincluding AEI-type, AEN-type, AFN-type, AFV-type, AFX-type, BEA-type,CHA-type, ERI-type, ETL-type, FAU-type (X-type, Y-type), GIS-type,LEV-type, LTA-type, MEL-type, MFI-type, MOR-type, PAU-type, RHO-type,SAT-type, and SOD-type.

The zeolite membrane 12 contains, for example, silicon (Si). Forexample, the zeolite membrane 12 may contain any two or more of Si,aluminum (Al), and phosphorus (P). The zeolite membrane 12 may containalkali metal. The alkali metal is, for example, sodium (Na) or potassium(K). When the zeolite membrane 12 contains Si atoms, an Si/Al ratio inthe zeolite membrane 12 is, for example, higher than or equal to 1 andlower than or equal to 100,000. The Si/Al ratio is preferably higherthan or equal to 5, more preferably higher than or equal to 20, and yetmore preferably higher than or equal to 100. This ratio is preferably ashigh as possible. The Si/Al ratio in the zeolite membrane 12 can beadjusted by, for example, adjusting the composition ratio of an Sisource and an Al source in a starting material solution, which will bedescribed later.

Next, one example of the procedure for producing the zeolite membranecomplex 1 will be described with reference to FIG. 4 . In the productionof the zeolite membrane complex 1, first, the support 11 is formed (stepS11). Specifically, first, green body that is a material for the support11 is prepared by kneading ceramic particles, an inorganic binder,water, a dispersant, and a thickener. Then, the green body is subjectedto extrusion molding so as to form a generally cylindrical compact. Thiscompact is then fired to obtain a generally cylindrical fired compact.Then, the outside surface of the fired compact is grinded into a supportmember. Thereafter, a porous ceramic membrane that has smaller porediameters than the pore diameters of the support member is formed as anintermediate layer on the outside surface of the support member, andanother porous ceramic membrane that has yet smaller pore diameters isformed as a surface layer on the intermediate layer. In this way, thesupport 11 having a multilayer structure is formed.

In the aforementioned preparation of the green body, for example, 0.1 to50 parts by mass (in the present embodiment, 20 parts by mass) of theinorganic binder is added to 100 parts by mass of the ceramic particles(in the present embodiment, alumina particles). The alumina particleshave a mean particle diameter of, for example, 1 μm to 200 μm, and inthe present embodiment, 50 μm. A firing temperature of theaforementioned compact is in the range of, for example, 1000° C. to1800° C., and in the present embodiment, 1250° C. A firing time of theaforementioned compact is, for example, in the range of 0.1 to 100hours, and in the present embodiment, one hour.

For example, the outside surface of the fired compact is grinded with abelt-type grinder by a belt centerless method using fixed abrasivegrains of a diamond grinding wheel. Various modifications may be made tothe grinding method and the type of the grinder, used in this grinding.The intermediate layer and the surface layer described above are, forexample, porous alumina membranes with thicknesses of severalmicrometers to several hundred micrometers. The intermediate layer andthe surface layer are formed by, for example, vacuum filtrationdeposition. Alternatively, the intermediate layer and the surface layermay be formed by other methods. The intermediate layer has a mean porediameter of, for example, 0.1 μm to 10 μm, and in the presentembodiment, 0.5 μm. The surface layer has a mean pore diameter of, forexample, 0.01 μm to 5 μm, and in the present embodiment, 0.1 μm.

Then, seed crystals that are used to produce the zeolite membrane 12 areprepared (step S12). For example, the seed crystals are acquired fromDDR-type zeolite powder synthesized by hydrothermal synthesis. Thiszeolite powder may be used as-is as seed crystals, or may be processedinto seed crystals by pulverization or other methods. Note that step S12may be performed in parallel with step S11, or may be performed beforestep S11.

Next, the seed crystals are deposited on the outside surface 112 of thesupport 11 (step S13). In step S13, for example, the seed crystals aredeposited by filtration on the support 11. Specifically, first, thelower-end opening of the support 11 that stands upright with the centralaxis J1 running parallel to the up-down direction is sealed in aliquid-tight manner, and the upper-end opening thereof is attached in aliquid-tight manner to a generally cylindrical opening member 83 made ofa liquid-tight material. Then, as illustrated in FIG. 5 , the support 11is inserted from the lower end side (i.e., the side on which a sealmember 82 is attached) into a reservoir 80 that stores a solution 81 inwhich the seed crystals are dispersed, and is immersed in the solution81. An upper-end opening of the opening member 83 attached to the upperend of the support 11 is located above the liquid level of the solution81, and the outside surface 112 of the support 11 is located within thesolution 81. Accordingly, a solvent in the solution 81 permeates throughthe support 11 from the outside surface 112 of the support 11 and movesto the inner flow path 111, as indicated by arrows pointing in theright-left direction in FIG. 5 . On the other hand, the seed crystals inthe solution 81 remain on and adhere to the outside surface 112 of thesupport 11 without permeating through the support 11. In this way, aseed-crystal-deposited support is prepared.

When step S13 has ended, the support 11 with the seed crystals depositedthereon is taken out of the solution 81 and dried. The dried support 11with the seed crystals deposited thereon is immersed in a startingmaterial solution. For example, the starting material solution isprepared by dissolving or dispersing substances such as an Si source anda structure-directing agent (hereinafter, also referred to as an “SDA”)in a solvent. The solvent in the starting material solution may be wateror alcohol such as ethanol. The SDA contained in the starting materialsolution may, for example, be an organic compound. For example,1-adamantanamine may be used as the SDA.

Then, using the seed crystals as nuclei, the DDR-type zeolite is grownby hydrothermal synthesis into the DDR-type zeolite membrane 12 on thesupport 11 (step S14). The temperature of the hydrothermal synthesis ispreferably in the range of 120° C. to 200° C., and for example, 160° C.The time of the hydrothermal synthesis is preferably in the range of 10hours to 100 hours, and for example, 30 hours.

When the hydrothermal synthesis has ended, the support 11 and thezeolite membrane 12 are rinsed with deionized water. After the rinsing,the support 11 and the zeolite membrane 12 are dried at, for example,80° C. After the support 11 and the zeolite membrane 12 have been dried,the zeolite membrane 12 is subjected to heat treatment so as to almostcompletely burn and remove the SDA in the zeolite membrane 12 and causemicropores in the zeolite membrane 12 to come through the membrane (stepS15). In this way, the aforementioned zeolite membrane complex 1 isobtained.

In the aforementioned production of the zeolite membrane complex 1, ifthe support 11 has a greatly varying support thickness, the amount ofseed crystals to be deposited in step S13 will also vary. Specifically,a thin portion of the support 11 with a small support thickness has lowresistance when the solvent in the above solution permeates through thesupport 11. This increases the amount of the solvent permeating throughthe thin portion of the support 11 and also increases the amount of seedcrystals deposited on the outside surface 112 of the thin portion of thesupport 11. On the other hand, a thick portion of the support 11 with alarge support thickness has high resistance when the solvent permeatesthrough the support 11. This reduces the amount of the solventpermeating through the thick portion of the support 11 and also reducesthe amount of seed crystals deposited on the outside surface 112 of thethick portion of the support 11. As a result, the zeolite membrane 12increases in thickness in portions of the zeolite membrane complex 1that have small support thicknesses, and the zeolite membrane 12decreases in thickness in portions of the zeolite membrane complex thathave large support thicknesses. Accordingly, variations occur in themembrane thickness of the zeolite membrane 12.

Table 1 shows the relation of variations in support thickness andvariations in the membrane thickness of the zeolite membrane 12 in thezeolite membrane complex 1. Generally cylindrical supports 11 accordingto Examples 1 to 7 have an outer diameter of 20 mm and a longitudinallength of 15 cm. The same applies to the support according toComparative Example 1. Zeolite membranes 12 according to Examples 1 to 3and a zeolite membrane according to Comparative Example 1 are DDR-typezeolite membranes. Zeolite membranes 12 according to Examples 4 and 5are CHA-type zeolite membranes. Zeolite membranes 12 according toExamples 6 and 7 are AEI-type zeolite membranes.

The zeolite membrane complexes 1 according to Examples 1 to 7 and thezeolite membrane complex according to the comparative example wereproduced by a production method approximately similar to the productionmethod illustrated in steps S11 to S15 described above. Detailedproduction conditions and the like will be described below.

For the production of the DDR-type zeolite membranes 12 according toExamples 1 to 3, in step S13, a slurry solution for seed deposition,prepared such that DDR-type zeolite seed crystals dispersed in water hada concentration of 0.1% by mass, was used as the aforementioned solution81. Then, the support 11 with the seed crystals deposited thereon wassubjected to through-circulation drying with predetermined conditions(at room temperature, at an air velocity of 5 m/sec, for 10 minutes). Instep S14, 88.0 g of 30% by weight of silica sol (trade name: SNOWTEX Smanufactured by Nissan Chemical Corporation), 6.59 g of ethylenediamine(produced by FUJIFILM Wako Pure Chemical Corporation), 1.04 g of1-adamantanamine (produced by Sigma-Aldrich, Japan), and 104.4 g ofdeionized water were mixed for preparation of the aforementionedstarting material solution. The zeolite membrane 12 was synthesized byhydrothermal synthesis for 10 hours in an oven set at 130° C. Theremoval of the SDA was implemented by heating the support 11 with thezeolite membrane 12 formed thereon at 450° C. for 50 hours in anelectric furnace. The same applies to the production of the DDR-typezeolite membrane according to Comparative Example 1.

For the production of the CHA-type zeolite membranes 12 according toExamples 4 and 5, in step S12, CHA-type zeolite seed crystals wereprepared by interzeolite conversion of a Y-type zeolite or byhydrothermal synthesis of an aluminosilicate solution or the like. Instep S13, a slurry solution for seed deposition, prepared such that theCHA-type zeolite seed crystals dispersed in water had a concentration of0.1% by mass, was used as the aforementioned solution 81. Then, thesupport 11 with the seed crystals deposited thereon was subjected tothrough-circulation drying conducted with predetermined conditions (atroom temperature, at an air velocity of 5 m/sec, for 10 minutes). Instep S14, 21.3 g of 30% by weight of silica sol (trade name: SNOWTEX Smanufactured by Nissan Chemical Corporation), 0.90 g of potassiumhydroxide (produced by FUJIFILM Wako Pure Chemical Corporation), 1.18 gof sodium aluminate (produced by FUJIFILM Wako Pure ChemicalCorporation), 3.58 g of 25% by mass of an N,N,N-trimethyl-1-ammoniumhydroxide solution (produced by SACHEM, INC.), and 173.1 g of deionizedwater were mixed for preparation of the aforementioned starting materialsolution. The zeolite membrane 12 was synthesized by hydrothermalsynthesis for 30 hours in an oven set at 160° C. The removal of the SDAwas implemented by heating the support 11 having the zeolite membrane 12formed thereon at 550° C. for 10 hours.

For the production of the AEI-type zeolite membranes 12 according toExamples 6 and 7, in step S12, AEI-type zeolite seed crystals wereprepared by hydrothermal synthesis of an aluminophosphate solution orthe like. In step S13, a slurry solution for seed deposition, preparedsuch that the AEI-type zeolite seed crystals dispersed in water had aconcentration of 0.1% by mass, was used as the aforementioned solution81. Then, the support 11 with the seed crystals deposited thereon wassubjected to through-circulation drying conducted with predeterminedconditions (at room temperature, at an air velocity of 2 m/sec to 7m/sec, for 30 minutes). In step S13, the application of the slurrysolution for seed position and the through-circulation drying wereconducted twice. In step S14, 4.72 g of aluminum tri-isopropoxide(produced by KANTO CHEMICAL CO., INC.), 30.71 g of 35% by mass of atetraethylammonium hydroxide solution (produced by Sigma-Aldrich,Japan), 8.41 g of 85% phosphoric acid (produced by Sigma-Aldrich,Japan), and 156.17 g of deionized water were mixed for preparation ofthe aforementioned starting material solution. The zeolite membrane 12was synthesized by hydrothermal synthesis at 150° C. for 30 hours. Theremoval of the SDA was implemented by heating the support 11 having thezeolite membrane 12 formed thereon at 400° C. for 10 hours.

TABLE 1 Variation in Variation in Support Membrane Type of ZeoliteThickness Thickness Membrane (A − B)/(A + B) |a − b|/((a + b)/2) Example1 DDR-type zeolite 0.09  3% membrane Example 2 DDR-type zeolite 0.18  4%membrane Example 3 DDR-type zeolite 0.28  7% membrane ComparativeDDR-type zeolite 0.36 14% Example 1 membrane Example 4 CHA-type zeolite0.09  4% membrane Example 5 CHA-type zeolite 0.28  8% membrane Example 6AEI-type zeolite 0.09  4% membrane Example 7 AEI-type zeolite 0.28  9%membrane

Variation in support thickness in Table 1 represents “(A−B)/(A+B)”described above in one cross-section of the support 11. That is, thevariation in support thickness corresponds to a value obtained bydividing the difference between the maximum value A and minimum value Bof the support thickness in one cross-section of the support 11 by thesum of the maximum value A and the minimum value B. The variation insupport thickness increases as this value increases.

Variation in membrane thickness in Table 1 represents a value obtainedby dividing the absolute value of the difference between membranethicknesses “a” and “b” by an arithmetical mean of the membranethicknesses “a” and “b” in the above cross-section of the support 11(i.e., “|a−b|/((a+b)/2)”), where “a” is the membrane thickness of agiven portion of the zeolite membrane 12 where the support thickness isthe maximum value A, and “b” is the membrane thickness of a givenportion of the zeolite membrane 12 where the support thickness is theminimum value B. In Table 1, this value is expressed in percentage. Thevariation in the membrane thickness of the zeolite membrane 12 increasesas this value increases.

The maximum value A and minimum value B of the support thickness and themembrane thicknesses “a” and “b”, described above, were obtained bycutting the support 11 along a plane perpendicular to the central axisJ1 and observing the cross section using a scanning electron microscope(SEM).

When the variation in support thickness, i.e., (A−B)/(A+B), is greaterthan 0.3 as in Comparative Example 1, the variation in the membranethickness of the DDR-type zeolite membrane 12, i.e., |a−b|/((a+b)/2), isgreater than 10%. On the other hand, when the variation in supportthickness, i.e., (A−B)/(A+B), is less than or equal to 0.3 as inExamples 1 to 3, the variation in the membrane thickness of the DDR-typezeolite membrane 12, i.e., |a−b|/((a+b)/2), is less than or equal to10%.

Similarly, with the CHA-type zeolite membrane 12, when the variation insupport thickness, i.e., (A−B)/(A+B), is less than or equal to 0.3, thevariation in the membrane thickness of the zeolite membrane 12, i.e.,|a−b|/((a+b)/2), is less than or equal to 10% (Examples 4 and 5).Similarly, with the AEI-type zeolite membrane 12, when the variation insupport thickness, i.e., (A−B)/(A+B), is less than or equal to 0.3, thevariation in the membrane thickness of the zeolite membrane 12, i.e.,|a−b|/((a+b)/2), is less than or equal to 10% (Examples 6 and 7).

Next, the separation of a mixture of substances using the zeolitemembrane complex 1 will be described with reference to FIGS. 6 and 7 .FIG. 6 is a diagram illustrating a separator 2. FIG. 7 is a diagramillustrating a procedure for separating a mixture of substances,performed by the separator 2.

The separator 2, in which a mixture of substances including a pluralityof types of fluids (i.e., gases or liquids) is supplied to the zeolitemembrane complex 1, separates a substance having high permeability inthe mixture of substances from the mixture of substances by causing thesubstance to permeate through the zeolite membrane complex 1. Forexample, the separator 2 may made the separation for the purpose ofextracting a substance having high permeability from the mixture ofsubstances, or for the purpose of condensing a substance having lowpermeability.

The mixture of substances (i.e., mixed fluid) may be a mixed gasincluding a plurality of types of gases, may be a mixed solutionincluding a plurality of types of liquids, or may be gas-liquidtwo-phase fluid including both gases and liquids.

In the separator 2, the CO₂ permeance of the zeolite membrane complex 1at temperatures of 20° C. to 400° C. is, for example, greater than orequal to 100 nmol/m²·s·Pa. The ratio (permeance ratio) between theamount of CO₂ permeance and the amount of CH₄ permeance (leakage) of thezeolite membrane complex 1 at temperatures of 20° C. to 400° C. is, forexample, higher than or equal to 100. The permeance and the permeanceratio are values for the case where a difference in the partial pressureof CO₂ between the supply side and the permeation side of the zeolitemembrane complex 1 is 1.5 MPa.

The mixture of substances includes, for example, one or more kinds ofsubstances including hydrogen (H₂), helium (He), nitrogen (N₂), oxygen(O₂), water (H₂O), water vapor (H₂O), carbon monoxide (CO), carbondioxide (CO₂), nitrogen oxide, ammonia (NH₃), sulfur oxide, hydrogensulfide (H₂S), sulfur fluoride, mercury (Hg), arsine (AsH₃), hydrocyanicacid (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acid,alcohol, mercaptans, ester, ether, ketone, and aldehyde.

Nitrogen oxide is a compound of nitrogen and oxygen. The aforementionednitrogen oxide is, for example, a gas called NO_(x) such as nitrogenmonoxides (NO), nitrogen dioxides (NO₂), nitrous oxide (also referred toas dinitrogen monoxide) (N₂O), dinitrogen trioxide (N₂O₃), dinitrogentetroxide (N₂O₄), or dinitrogen pentoxide (N₂O₅).

Sulfur oxide is a compound of sulfur and oxygen. The aforementionedsulfur oxide is, for example, a gas called SO_(x) such as sulfur dioxide(SO₂) or sulfur trioxide (SO₃).

Sulfur fluoride is a compound of fluorine and sulfur. The aforementionedsulfur fluoride may, for example, be disulfur difluoride (F—S—S—F,S═SF₂), sulfur difluoride (SF₂), sulfur tetrafluoride (SF₄), sulfurhexafluoride (SF₆), or disulfur decafluoride (S₂F₁₀).

C1 to C8 hydrocarbons are hydrocarbons containing one or more and eightor less carbon atoms. C3 to C8 hydrocarbons each may be any of alinear-chain compound, a side-chain compound, and a cyclic compound. C2to C8 hydrocarbons each may be either a saturated hydrocarbon (i.e., theabsence of a double bond and a triple bond in a molecule) or anunsaturated hydrocarbon (i.e., the presence of a double bond and/or atriple bond in a molecule). C1 to C4 may, for example, be methane (CH₄),ethane (C₂H₆), ethylene (C₂H₄), propane (C₃H₈), propylene (C₃H₆), normalbutane (CH₃(CH₂)₂CH₃), isobutane (CH(CH₃)₃), 1-butene (CH₂═CHCH₂CH₃),2-butene (CH₃CH═CHCH₃), or isobutene (CH₂═C(CH₃)₂).

The aforementioned organic acid may, for example, be carboxylic acid orsulfonic acid. The carboxylic acid may, for example, be formic acid(CH₂O₂), acetic acid (C₂H₄O₂), oxalic acid (C₂H₂O₄), acrylic acid(C₃H₄O₂), or benzoic acid (C₆H₅COOH). The sulfonic acid may, forexample, be ethane sulfonic acid (C₂H₆O₃S). The organic acid may beeither a chain compound or a cyclic compound.

The aforementioned alcohol may, for example, be methanol (CH₃OH),ethanol (C₂H₅OH), isopropanol (2-propanol) (CH₃CH(OH)CH₃), ethyleneglycol (CH₂(OH)CH₂(OH)), or butanol (C₄H₉OH).

The mercaptans are organic compounds with terminal sulfur hydride (SH)and are substances called also thiol or thioalcohol. The aforementionedmercaptans may, for example, be methyl mercaptans (CH₃SH), ethylmercaptans (C₂H₅SH), or 1-propane thiol (C₃H₇SH).

The aforementioned ester may, for example, be formic acid ester oracetic acid ester.

The aforementioned ether may, for example, be dimethyl ether ((CH₃)₂O),methyl ethyl ether (C₂H₅OCH₃), or diethyl ether ((C₂H₅)₂O).

The aforementioned ketone may, for example, be acetone ((CH₃)₂CO),methyl ethyl ketone (C₂H₅COCH₃), or diethyl ketone ((C₂H₅)₂CO).

The aforementioned aldehyde may, for example, be acetaldehyde (CH₃CHO),propionaldehyde (C₂H₅CHO), or butanal (butyraldehyde) (C₃H₇CHO).

The following description takes the example of the case where themixture of substances to be separated by the separator 2 is a mixed gasincluding a plurality of types of gases.

The separator 2 includes the zeolite membrane complex 1, sealers 21, anouter cylinder 22, seal member 23, a supply part 26, a first collectingpart 27, and a second collecting part 28. The zeolite membrane complex1, the sealer 21, and the seal members 23 are placed in the outercylinder 22. The supply part 26, the first collecting part 27, and thesecond collecting part 28 are disposed outside the outer cylinder 22 andconnected to the outer cylinder 22.

The sealers 21 are members mounted on the both ends of the support 11 inthe longitudinal direction (i.e., left-right direction in FIG. 6 ) andcovering and sealing the both end faces of the support 11 in thelongitudinal direction and the outside surface of the support 11 in thevicinity of the both end faces. The sealers 21 prevent the inflow andoutflow of gases from the opposite generally ring-shaped both end facesof the support 11. The sealers 21 are, for example, plate-like membersformed of glass or resin. The material and shape of the sealers 21 maybe appropriately changed. The right sealer 21 in FIG. 6 has an openingthat overlaps with the inner flow path 111 of the support 11, andtherefore a right end opening of the inner flow path 111 is not coveredwith the sealer 21. Accordingly, the gas in the inner flow path 111 canflow out from this end opening to the outside of the zeolite membranecomplex 1. On the other hand, the left sealer 21 in FIG. 6 has noopening, and therefore the gas cannot flow in and out through the leftend of the inner flow path 111.

The outer cylinder 22 is a generally cylindrical tubular member. Theouter cylinder 22 is formed of, for example, stainless steel or carbonsteel. The longitudinal direction of the outer cylinder 22 isapproximately parallel to the longitudinal direction of the zeolitemembrane complex 1 (i.e., direction pointing in the central axis J1).The outer cylinder 22 has a supply port 221 and a first exhaust port 222on the outside surface. The supply port 221 and the first exhaust port222 are, for example, arranged on the opposite sides in the radialdirection with the zeolite membrane complex 1 sandwiched therebetween(i.e., at 180° different positions in the circumferential direction).The outer cylinder 22 also has a second exhaust port 223 on one end inthe longitudinal direction (i.e., right end in FIG. 6 ). The supply port221 is connected to the supply part 26. The first exhaust port 222 isconnected to the first collecting part 27. The second exhaust port 223is connected to the second collecting part 28. An internal space of theouter cylinder 22 is an enclosed space isolated from the space aroundthe outer cylinder 22.

The seal member 23 is arranged around the entire circumference betweenthe outside surface of the zeolite membrane complex 1 and the insidesurface of the outer cylinder 22 in the vicinity of an end of thezeolite membrane complex 1 in the longitudinal direction. The sealmember 23 is a generally ring-shaped member formed of a material that isimpermeable to gases. For example, the seal member 23 is O-ring formedof a resin having flexibility. The seal member 23 is in tight contactwith the outside surface of the zeolite membrane complex 1 and theinside surface of the outer cylinder 22 around the entire circumference.In the example illustrated in FIG. 6 , the seal member 23 is in tightcontact with the outside surface of the right sealer 21 in the drawingand is indirectly in tight contact with the outside surface of thezeolite membrane complex 1 via this sealer 21. A space between the sealmember 23 and the outside surface of the zeolite membrane complex 1 anda space between the seal member 23 and the inside surface of the outercylinder 22 are sealed so as to almost or completely disable the passageof gases. Note that the seal member 23 may be provided between the outercylinder 22 and an end face of the zeolite membrane complex 1 in thelongitudinal direction.

The supply part 26 supplies a mixed gas to the internal space of theouter cylinder 22 through the supply port 221. For example, the supplypart 26 is a blower or pump that transmits the mixed gas toward theouter cylinder 22 under pressure. The blower or pump includes a pressureregulator that regulates the pressure of the mixed gas supplied to theouter cylinder 22. The first collecting part 27 and the secondcollecting part 28 are, for example, reservoirs that store the gasderived from the outer cylinder 22, or are blowers or pumps thattransfer the gas.

In the case of separating a mixed gas, the aforementioned separator 2 isprovided to prepare the zeolite membrane complex 1 (step S21). Then, thesupply part 26 supplies a mixed gas that includes a plurality of typesof gases having different permeability to the zeolite membrane 12, tothe internal space of the outer cylinder 22. For example, the mixed gasis composed predominantly of CO₂ and CH₄. The mixed gas may also includeother gases different from CO₂ and CH₄. The pressure of the mixed gassupplied from the supply part 26 to the internal space of the outercylinder 22 (i.e., supply pressure) is, for example, in the range of 0.1MPa to 20.0 MPa. The temperature of separating the mixed gas is, forexample, in the range of 10° C. to 150° C.

The mixed gas supplied from the supply part 26 to the outer cylinder 22flows toward the outside surface of the zeolite membrane complex 1, asindicated by an arrow 251. A gas having high permeability (e.g., CO₂ andhereinafter referred to as a “high-permeability substance”) in the mixedgas permeates through the zeolite membrane 12 provided on the outsidesurface 112 of the support 11 and through the support 11, and is thenemitted from the inside surface 113 of the support 11 to the inner flowpath 111. Accordingly, the high-permeability substance is separated froma gas having low permeability (e.g., CH₄ and hereinafter referred to asa “low-permeability substance”) in the mixed gas (step S22). The gasemitted from the inside surface 113 of the support 11 to the inner flowpath 111 (hereinafter referred to as a “permeated substance”) iscollected by the second collecting part 28 through the second exhaustport 223, as indicated by an arrow 253. The pressure (i.e., permeationpressure) of the gas collected by the second collecting part 28 throughthe second exhaust port 223 is, for example, approximately oneatmospheric pressure (0.101 MPa). The permeated substance may include asubstance other than the aforementioned high-permeability substance.

In the mixed gas, a gas other than the gas having permeated through thezeolite membrane 12 and the support 11 (hereinafter, referred to as a“non-permeated substance”) passes through the space between the outsidesurface of the zeolite membrane complex 1 and the inside surface of theouter cylinder 22 from the upper side to the lower side in the drawingand is collected by the first collecting part 27 through the firstexhaust port 222, as indicated by an arrow 252. The pressure of the gascollected by the first collecting part 27 through the first exhaust port222 is, for example, approximately the same pressure as the supplypressure. The non-permeated substance may also include ahigh-permeability substance that has not permeated through the zeolitemembrane 12, in addition to the aforementioned low-permeabilitysubstance.

As described above, the porous cylindrical support 11 used to supportthe zeolite membrane 12 has the generally cylindrical inside surface 113having the central axis J1 extending in the longitudinal direction asits center, and the generally cylindrical outside surface 112surrounding the inside surface 113. The zeolite membrane 12 is formed onthe outside surface 112. The radial distance between the inside surface113 and the outside surface 112, i.e., the maximum value A and theminimum value B in the circumferential direction of the thickness of thesupport, satisfy (A−B)/(A+B)≤0.3 in at least part of the support 11 inthe longitudinal direction.

By reducing the variation in the support thickness in this way, asdescribed previously, it is possible for the support 11 to improveuniformity in the membrane thickness of the zeolite membrane 12 formedon the support 11. Accordingly, even in the case where the zeolitemembrane 12 is formed to a small mean thickness, it is possible toprevent part of the zeolite membrane 12 from becoming a defect bybecoming too thin. As a result, the dense and thin zeolite membrane 12can be formed on the support 11.

As described above, it is preferable for the support 11 that the maximumvalue A and the minimum value B of the support thickness in thecircumferential direction satisfy (A−B)/(A+B)≤0.3 along the entirelength of the support 11 in the longitudinal direction. This furtherimproves uniformity in the membrane thickness of the zeolite membrane 12formed on the support 11.

As described above, it is preferable for the support 11 that the maximumvalue A and the minimum value B of the support thickness in thecircumferential direction satisfy (A−B)/(A+B)≤0.2, and in particular(A−B)/(A+B)≤0.1 in at least part of the support 11 in the longitudinaldirection. This further improves uniformity in the membrane thickness ofthe zeolite membrane 12 formed on the support 11.

As described above, it is more preferable for the support 11 that themaximum value A and the minimum value B of the support thickness in thecircumferential direction satisfy (A−B)/(A+B)≤0.2, and in particular(A−B)/(A+B)≤0.1, along the entire length of the support 11 in thelongitudinal direction. This further improves uniformity in the membranethickness of the zeolite membrane 12 formed on the support 11.

As described above, it is preferable for the support 11 that the meanradius X and the roundness Y of the inside surface 113 satisfy Y/X≤0.5,yet more preferably Y/X≤0.3, and in particular Y/X≤0.1, in at least partof the support 11 in the longitudinal direction. In this way, if thecross-sectional shape of the inside surface 113 perpendicular to thecentral axis J1 is relatively close to a perfect circle, it is possibleto improve uniformity in support thickness in the circumferentialdirection when the outside surface 112 is made closer to a perfectcircle by grinding or other methods at the time of forming the support11. Accordingly, the support 11, at least part of which in thelongitudinal direction satisfies (A−B)/(A+B)≤0.3, can be formed withhigh yields.

As described above, it is more preferable for the support 11 that themean radius X and the roundness Y of the inside surface 113 satisfyY/X≤0.5, yet more preferably Y/X≤0.3, and in particular Y/X≤0.1, alongthe entire length of the support 11 in the longitudinal direction.Accordingly, the support 11 that satisfies (A−B)/(A+B)≤0.3 along theentire length in the longitudinal direction can be formed with higheryields.

As described above, the support 11 is preferably formed of a ceramicsintered compact. This enables increasing the strength of bondingbetween the zeolite membrane 12 and the support 11 more than in the casewhere the support is formed of a material other than a ceramic sinteredcompact, and thereby enables stably supporting the zeolite membrane 12.

The zeolite membrane complex 1 includes the aforementioned support 11,and the zeolite membrane 12 formed on the outside surface 112 of thesupport 11. This enables providing the zeolite membrane complex 1 thatincludes the zeolite membrane 12 having high uniformity in membranethickness. Accordingly, it is also possible to provide the zeolitemembrane complex 1 that includes the dense and thin zeolite membrane 12.In other words, the zeolite membrane complex 1 can reduce the thicknessof the zeolite membrane 12.

Since, as described above, the zeolite membrane complex 1 can reduce thethickness of the zeolite membrane 12, the structure of the zeolitemembrane complex 1 is in particular suitable for use as a zeolitemembrane complex that includes a zeolite membrane 12 having a thicknessless than or equal to 1 μm (minimum membrane thickness).

As described above, a maximum number of membered rings in the zeolite ofthe zeolite membrane 12 is preferably less than or equal to 8.Accordingly, when the zeolite membrane 12 is used for the separation ofa mixture of substances, it is possible to favorably achieve selectivepermeation of a to-be-permeated substance having a relatively smallmolecular diameter, such as CO₂, and to efficiently separate theto-be-permeated substance from the mixture of substances.

The aforementioned method of producing the zeolite membrane complex 1includes the step of preparing seed crystals (step S12), the step ofdepositing the seed crystals on the support 11 (step S13), and the stepof forming the zeolite membrane 12 on the support 11 by growing azeolite from the seed crystals by hydrothermal synthesis (step S14).Accordingly, it is possible to provide the zeolite membrane complex 1that includes the zeolite membrane 12 having high uniformity in membranethickness. It is also possible to provide the zeolite membrane complex 1that includes the dense and thin zeolite membrane 12.

The aforementioned separation method includes the step of preparing theabove-described zeolite membrane complex 1 (step S21), and the step ofsupplying a mixture of substances including a plurality of types ofgases or liquids to the zeolite membrane 12 and separating a substancewith high permeability in the mixture of substances from the mixture ofsubstances by causing the substance with high permeability to permeatethrough the zeolite membrane complex 1 (step S22). This enablesfavorably separating a substance with high permeability (i.e.,high-permeability substance) from the mixture of substances.

This separation method is in particular suitable for use in theseparation of a mixture of substances including one or more kinds ofsubstances including hydrogen, helium, nitrogen, oxygen, water, watervapor, carbon monoxide, carbon dioxide, nitrogen oxide, ammonia, sulfuroxide, hydrogen sulfide, hydrogen fluoride, mercury, arsine, hydrocyanicacid, carbonyl sulfide, C1 to C8 hydrocarbons, organic acid, alcohol,mercaptans, ester, ether, ketone, and aldehyde.

The support 11, the zeolite membrane complex 1, the method of producingthe zeolite membrane complex 1, and the separation method for a mixtureof substances, described above, may be modified in various ways.

For example, the support 11 does not necessarily have to be formed of aceramic sintered compact, and may be formed of other materials such asmetal. The mean radius X and the roundness Y of the inside surface 113of the support 11 do not necessarily have to satisfy Y/X≤0.5. Thecentral axis of the outside surface 112 of the support 11 does notnecessarily have to match the central axis J1 of the inside surface 113,and may be different from the central axis J1.

In the zeolite membrane complex 1, the membrane thickness of the zeolitemembrane 12 is not limited to be less than or equal to 1 and may bemodified in various ways. A maximum number of membered rings in thezeolite of the zeolite membrane 12 may be greater than 8, or may besmaller than 8.

The aforementioned support 11 may be produced by a production methoddifferent from the method described in the above example. For example,the outside surface does not necessarily have to be grinded.

The aforementioned zeolite membrane complex 1 may be produced by aproduction method different from the method described in the aboveexample. For example, a technique different from the technique describedin the above example may be used to deposit seed crystals on the support11. The zeolite membrane 12 may be formed on the inside surface 113 ofthe support 11, or may be formed on both of the outside surface 112 andthe inside surface 113 of the support 11.

The structure of the separation apparatus 2 illustrated in FIG. 6 may bemodified in various ways. For example, like the right sealer 21 in FIG.6 , the left sealer 21 in FIG. 6 may also have an opening that overlapswith the inner flow path 111, and seal member 23 may be provided forsealing. Also, the left end face of the outer cylinder 22 may also havea second exhaust port 223 that is connected to the second collectingpart 28.

The separator 2 and the separation method described above may separate asubstance other than the substance exemplified in the above descriptionfrom a mixture of substances.

The zeolite membrane 12 in the zeolite membrane complex 1 does notnecessarily have to be used for the separation of a high-permeabilitysubstance from a mixture of substances, and may be used in otherapplications such as for use as an absorption membrane or apervaporation membrane.

The configurations of the preferred embodiments and variations describedabove may be appropriately combined as long as there are no mutualinconsistencies.

While the invention has been shown and described in detail, theforegoing description is in all aspects illustrative and notrestrictive. It is therefore understood that numerous modifications andvariations can be devised without departing from the scope of theinvention.

INDUSTRIAL APPLICABILITY

The support according to the present invention is, for example,applicable for use in supporting a zeolite membrane that can be used asa gas separation membrane. The zeolite membrane complex according to thepresent invention is applicable in various fields that use zeolites,such as for use as a gas separation membrane, a separation membrane forsubstances other than gases, and an adsorption membrane for varioussubstances.

REFERENCE SIGNS LIST

-   -   1 Zeolite membrane complex    -   11 Support    -   12 Zeolite membrane    -   112 Outside surface (of support)    -   113 Inside surface (of support)    -   A Maximum value (for support thickness in circumferential        direction)    -   B Minimum value (for support thickness in circumferential        direction)    -   J1 Central axis    -   S11 to S15, S21, and S22 Step

1. A zeolite membrane complex comprising: a porous cylindrical supportcomprising a generally cylindrical inside surface having a central axisextending in a longitudinal direction, and a generally cylindricaloutside surface that surrounds said inside surface, wherein a maximumvalue A and a minimum value B of a support thickness in acircumferential direction satisfy (A−B)/(A+B)≤0.3 in at least part ofthe support in the longitudinal direction, the support thickness being aradial distance between said inside surface and said outside surface;and a zeolite membrane formed on said support.
 2. The zeolite membranecomplex according to claim 1, wherein a maximum number of membered ringsin a zeolite of said zeolite membrane is less than or equal to
 8. 3. Thezeolite membrane complex according to claim 1, wherein said zeolitemembrane has a thickness less than or equal to 1 μm.
 4. A method ofproducing a zeolite membrane complex, comprising: a) preparing seedcrystals; b) depositing said seed crystals on the support according toclaim 1; and c) forming a zeolite membrane on said support by growing azeolite from said seed crystals by hydrothermal synthesis.
 5. Aseparation method comprising: d) preparing the zeolite membrane complexaccording to claim 1; and e) supplying a mixture of substances thatincludes a plurality of types of gases or liquids to said zeolitemembrane complex and separating a high-permeability substance in saidmixture of substances from said mixture of substances by causing saidhigh-permeability substance to permeate through said zeolite membranecomplex.
 6. The separation method according to claim 5, wherein saidmixture of substances includes one or more kinds of substances includinghydrogen, helium, nitrogen, oxygen, water, water vapor, carbon monoxide,carbon dioxide, nitrogen oxide, ammonia, sulfur oxide, hydrogen sulfide,sulfur fluoride, mercury, arsine, hydrocyanic acid, carbonyl sulfide, C1to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether,ketone, and aldehyde.